WO2000079020A1 - Film de carbone, procede de formation associe, article recouvert de ce film, et procede de preparation de cet article - Google Patents

Film de carbone, procede de formation associe, article recouvert de ce film, et procede de preparation de cet article Download PDF

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Publication number
WO2000079020A1
WO2000079020A1 PCT/JP2000/003886 JP0003886W WO0079020A1 WO 2000079020 A1 WO2000079020 A1 WO 2000079020A1 JP 0003886 W JP0003886 W JP 0003886W WO 0079020 A1 WO0079020 A1 WO 0079020A1
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WIPO (PCT)
Prior art keywords
gas
plasma
chamber
carbon film
film
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Application number
PCT/JP2000/003886
Other languages
English (en)
Japanese (ja)
Inventor
Yasuo Murakami
Takahiro Nakahigashi
Jo Takeuchi
Original Assignee
Nissin Electric Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP11172130A external-priority patent/JP2000096233A/ja
Application filed by Nissin Electric Co., Ltd. filed Critical Nissin Electric Co., Ltd.
Priority to US09/744,985 priority Critical patent/US6652969B1/en
Priority to EP00939067A priority patent/EP1114881A4/fr
Publication of WO2000079020A1 publication Critical patent/WO2000079020A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
    • C23C16/0245—Pretreatment of the material to be coated by cleaning or etching by etching with a plasma
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer

Definitions

  • the present invention relates to a carbon film, particularly carbon, a carbon film containing fluorine and hydrogen, a carbon film containing hydrogen and nitrogen, hydrogen, and a metal simple substance, a metal compound, a silicon simple substance, and a silicon compound.
  • the present invention relates to a carbon film containing at least one of them, a method for forming the same, and a carbon film-coated article and a method for producing the same.
  • a carbon film is known as a material that imparts necessary hardness while imparting a certain degree of lubricity to the surface of an article. Carbon films are also used as coatings on mechanical parts for the purpose of imparting wear resistance.
  • DLC film diamond-like carbon film
  • diamond-like carbon film diamond-like carbon film
  • the carbon film-coated substrate can be formed with good adhesion to the extent that the original flexibility of the substrate is not impaired. It can be easily formed at a relatively low temperature by a plasma CVD method or the like.
  • lubricating fluorides such as polytetrafluoroethylene are not very hard. Therefore, although the coating film, sheet, film and the like can be used stably for a long period of time as compared with lubricating oil and the like, because of their softness, they are liable to wear or break and fall from the article body. Easy to do.
  • some articles have an article surface formed of an elastic material depending on the intended use, but the coating film, sheet, film, and the like formed on such an elastically deformable portion are There is also a problem in that the article is liable to peel off due to elastic deformation.
  • Lubricating material pieces that have fallen off an article may penetrate the sliding surface with another article, causing an unexpected situation (for example, a malfunction of the machine).
  • the carbon film is superior to the lubricating fluoride in terms of wear resistance, adhesion to an article, and the like, but is still required to be improved in slidability (lubricity) with other articles. Sometimes.
  • the substrate may be used. In some cases, it is desirable to further increase the hardness of the carbon film in order to further enhance the surface modification effect of the carbon film.
  • An object of the present invention is to provide a carbon film which has a higher hardness than conventional lubricating fluorides, has excellent abrasion resistance, and can be formed with better adhesion to articles than lubricating fluorides, and a method for forming the same. It is to provide.
  • Another object of the present invention is that the hardness is higher than the conventional lubricating fluoride, the abrasion resistance is excellent, the lubricating property is better than the conventional carbon film, and the adhesion to the article is higher than the lubricating fluoride.
  • An object of the present invention is to provide a carbon film that can be formed well and a method for forming the carbon film.
  • Still another object of the present invention is to provide a carbon film which is higher in hardness and abrasion resistance than conventional lubricating fluorides, and has good adhesion to articles compared to lubricating fluorides. It is an object of the present invention to provide a carbon film-coated article having high durability and a method for producing the same.
  • Still another object of the present invention is to have higher hardness and wear resistance as compared with conventional lubricating fluorides, more lubricious as compared with conventional carbon films, and as compared with lubricating fluorides. It is intended to provide a carbon film-coated article which is coated with a carbon film having good adhesion to an article and has high durability, and a method for producing the same. Disclosure of the invention
  • the present invention provides the following carbon film and carbon film-coated article, and a method for forming a carbon film and a method for producing a carbon film-coated article.
  • a carbon film containing fluorine and hydrogen A carbon film containing fluorine and hydrogen.
  • 100 cm derived from a C-F bond is 100 cm- 0 0 cm- 1 peak area (IR ⁇ C-F) and 2800 cm- 1 to 3100 cm-'peak area (IR ⁇ C-H) derived from C-H bond the ratio of the (IR ⁇ C- F) / ( IR, C - H) is 0 yo Ri rather large, and, in due Rusupeku torr XPS (X-ray photoelectron spectroscopy), derived from the F 1 S A carbon film in which the ratio (F 1 S ZC 1 S ) between the peak intensity and the peak intensity derived from C 1 S is larger than 0 and smaller than 3.
  • a method for forming a carbon film containing fluorine and hydrogen in which a substrate for forming a carbon film is installed in a film formation chamber, and a hydrocarbon compound gas and fluorine are used as film formation gases in the film formation chamber. While introducing a gas containing a carbonized compound gas, the pressure in the film formation chamber is maintained at a predetermined pressure, the gas is turned into plasma under electric power supply, and fluorine and the fluorine are deposited on the substrate under the plasma. A carbon film containing hydrogen is formed, and when the hydrocarbon compound gas and the carbon fluoride compound gas are introduced, by adjusting the mixing ratio of the two gases, the obtained carbon film is converted into a FT film.
  • a method for forming a carbon film containing hydrogen and nitrogen in which a substrate for forming a carbon film is installed in a film forming chamber, and a hydrocarbon compound gas and a gas containing nitrogen are used as film forming gases in the film forming chamber. While introducing a gas containing, the pressure in the film forming chamber is maintained at a predetermined pressure, the gas is turned into a plasma under electric power supply, and a carbon film containing hydrogen and nitrogen is formed on the substrate under the plasma.
  • the carbon film forming method to be formed.
  • a method for forming a carbon film containing hydrogen and one or more of a simple metal, a metal compound, a simple silicon, and a silicon compound A base for forming a carbon film is formed in a film formation chamber. And a gas for forming one or more of a metal simple substance, a metal compound, a silicon simple substance, and a silicon compound in the film forming chamber as a film forming gas. While introducing a gas containing, the pressure in the film formation chamber is maintained at a predetermined pressure, the gas is turned into a plasma under the supply of electric power, and hydrogen, a metal unit, and a metal are deposited on the substrate under the plasma.
  • a carbon film forming method for forming a carbon film containing one or more of a compound, a simple substance of silicon, and a silicon compound A carbon film forming method for forming a carbon film containing one or more of a compound, a simple substance of silicon, and a silicon compound.
  • a film forming chamber including a plasma processing chamber connected in series is employed, a base for forming a carbon film is installed in the plasma processing chamber, and a single metal, a metal compound, and silicon are provided in the plasma generating chamber.
  • a sputter target composed of one or more of a single substance and a silicon compound is arranged, a hydrocarbon compound gas is introduced into the plasma processing chamber, and a sputter target is formed in the plasma generation chamber. Introduce gas.
  • the sputtering gas introduced into the plasma generation chamber is converted into a plasma under electric power supply, and the plasma and the sputter target are generated by the sputtering of the sputtering target based on the plasma.
  • Sputter particles are introduced into the plasma processing chamber, and the The hydrocarbon compound gas introduced into the plasma processing chamber is decomposed (plasmaized), and hydrogen and one or more of a metal simple substance, a metal compound, a silicon simple substance, and a silicon compound are deposited on the substrate.
  • the sputtering gas introduced into the plasma generation chamber is converted into a plasma under the supply of electric power, and the shower gate is snorted with the plasma.
  • the hydrocarbon compound gas introduced into the plasma processing chamber is also turned into a plasma under power supply, and hydrogen and a simple metal, a metal compound, A carbon film forming method for forming a carbon film containing one or more of a silicon simple substance and a silicon compound.
  • FIG. 1 is a diagram showing a schematic configuration of an example of a film forming apparatus that can be used for manufacturing a carbon film and a carbon film-coated article according to the present invention.
  • FIG. 2 is a diagram showing a schematic configuration of another example of a film forming apparatus that can be used for manufacturing a carbon film and a carbon film-coated article according to the present invention.
  • FIG. 3 is a diagram showing a schematic configuration of still another example of a film forming apparatus that can be used for manufacturing a carbon film and a carbon film-coated article according to the present invention.
  • FIG. 4 is a sectional view of an example of the carbon film-coated article according to the present invention.
  • FIG. 5 is a diagram showing the relationship between the introduction flow rate ratio between the hydrocarbon compound gas and the carbon fluoride gas, which are the film forming gases, and the film forming speed.
  • Figure 6 shows the introduction flow rates of the hydrocarbon compound gas and the fluorocarbon compound gas, which are the deposition gases, and the spectrum of the carbon film formed based on those flow ratios, as measured by FT-IR spectroscopy.
  • FIG. 7 is a diagram showing the XPS spectrum of the carbon film formed based on the introduction flow ratios of the hydrocarbon compound gas and the fluorocarbon compound gas, which are the film forming gases, and the flow ratios.
  • FIG. 9 is a diagram showing the relationship between the introduction flow ratio of the hydrocarbon compound gas and the carbon fluoride gas, which are the film forming gases, and the friction coefficient of the carbon film.
  • FIG. 10 is a graph showing the relationship between the introduction flow ratio of the hydrocarbon compound gas and the fluorocarbon compound gas, which are the film forming gases, and the hardness (Vickers hardness) of the carbon film.
  • FIG. 11 is a diagram showing the relationship between the introduction flow ratio of the hydrocarbon compound gas, which is a film forming gas, to the carbon fluoride compound gas, and the water repellency (water repellency, contact angle) of the carbon film.
  • FIG. 12 is a diagram showing the relationship between the modulation frequency of the high-frequency power for gas plasma generation and (F 1 S / C 1 S ) by XPS of the carbon film formed based on the modulation frequency.
  • Figures 1 to 3 the duty of frequency modulation of the high-frequency gas plasma power, the relationship between the the modulation frequency also by XPS of the carbon film formed on preparative (F 1 S / C 1 S ) and water-repellent FIG.
  • FIG. 14 (A) is a diagram showing a schematic configuration of still another example of a film forming apparatus that can be used for manufacturing the carbon film and the carbon film-coated article according to the present invention
  • FIG. FIG. 15 is a view showing another example of the power supply electrode for plasma generation in the apparatus shown in FIG. 14 (A).
  • the carbon film formed on the article by the method for producing a carbon film-coated article described above (hereinafter, these may be referred to as “fluorine-hydrogen-containing carbon film”) has a C-F bond portion, In other words, it is a carbon film in which fluoride is mixed.It has both lubricating properties to a certain extent and a carbon film part having a higher hardness than fluoride and a C-F bond part having more lubricity than the carbon film part. As a result, it has excellent lubricity, hardness, and wear resistance as a whole.
  • the carbon film-coated article according to the above (2) which is coated with the fluorine- and hydrogen-containing carbon film, has high durability.
  • the fluorine-hydrogen-containing carbon film according to the present invention requires the presence of C-F bonds, and if it is too large, the hardness of the entire film is reduced and the wear resistance is reduced.
  • FT-IR Fastier transform infrared
  • a peak area of 100 cm- 1 to 1300 cm— ′ derived from C—F bond (IR ⁇ C -F) and the ratio of the peak area (IR-C-H) of 2800 cm- 1 to 310 cm- 'derived from the C-H bond (IR-C-F) / (IR- C—H) is greater than 0, and the ratio of the peak intensity derived from F 1 S to the peak intensity derived from C 1 S (F 1S ) in the XPS (X-ray photoelectron spectroscopy) spectrum / C 1 S ) is a carbon film larger than 0 and smaller than 3.
  • the fluorine-hydrogen-containing carbon film according to the present invention may further contain nitrogen in order to further increase the hardness.
  • a simple metal, a metal compound typically, a metal oxide, a metal nitride, or a metal carbide
  • a silicon simple substance typically, a silicon compound (typically, a silicon oxide, a silicon oxide)
  • a silicon compound typically, a silicon oxide, a silicon oxide
  • One or more of nitrides and silicon carbide May be contained.
  • the ratio of C-F bonds in the thickness direction of the film increases or decreases continuously or stepwise in order to enhance the adhesion to the article and further satisfy both the hardness, wear resistance, and lubricity. It may be changed to do so.
  • the ratio of C-F bonds is increased continuously or stepwise from the side closer to the substrate or the article body in the thickness direction of the film.
  • the carbon film changes to
  • the fluorine-containing hydrogen-containing carbon film according to the present invention may have a predetermined hardness, but a DLC (diamond-1 ike carbon) film may be mentioned as a typical example. it can.
  • the DLC film has excellent slidability (lubricity) with other objects, abrasion resistance, electrical insulation, water repellency, and the like, and has a light-transmitting property at a normal film thickness. Further, by adjusting the film thickness, even if the film-formed surface of the substrate or article covered with the carbon film is made of a flexible material such as rubber or resin, the film thickness can be controlled by controlling the film thickness. It can be formed with good adhesion without impairing the flexibility of the substrate or the article. Further, it can be easily formed at a relatively low temperature by a plasma CVD method or the like.
  • Examples of the method of forming the carbon film in the carbon film described in (1) above and the carbon film-coated article in (2) above include a plasma CVD method, a sputtering method, an ion plating method and the like.
  • the plasma CVD method has an advantage that pretreatment by plasma and formation of a carbon film described later can be performed using the same apparatus.
  • film forming methods such as plasma CVD, sputtering, and ion plating use a relatively heat-resistant material such as rubber or resin as a material for a carbon film forming substrate or a film-forming surface of a film-forming article. Even when a material having poor properties is used, there is an advantage that a film can be formed within a temperature range that does not cause thermal damage to the material.
  • the film forming pressure is not limited to, for example, about 100 mTorr, and when the film forming temperature is set to 100 ° C. or lower, the DLC film is formed. It is formed. As the film formation temperature is increased, the hardness of the formed film is improved, and at 500 ° C. or more, a carbon film having extremely excellent wear resistance is formed. At 900 ° C. or higher, a diamond film is formed.
  • Hydrocarbon compound gases that can be used for forming a carbon film in these methods include methane (CH 4 ), ethane (C 2 H), and propyl (C 3 H 8), porcine emissions (C 4 H,.), acetylene (C 2 H), benzene (C beta Eta), according to gas and needs of hydrocarbon compounds such as hexane (C 6 H 12) cyclohexane, A mixture of these hydrocarbon compound gases with a hydrogen gas, an inert gas, or the like as a carrier gas can be used.
  • fluorocarbon compound gas examples include carbon tetrafluoride (CF 4 ) gas, carbon hexafluoride (C 2 F) gas, and carbon tetrafluoride (C 4 F 8 ) gas. It can.
  • the use of a mixture of a hydrocarbon compound gas and a fluorocarbon compound gas not only improves the lubricity of the obtained carbon film but also increases the film formation rate.
  • the productivity can be improved, and the effect of improving the film adhesion and the gas barrier property by reducing the film stress can be obtained.
  • a gas containing a nitrogen-containing gas (N 2 , ammonia, hydrazine, or the like) may be used to form a nitrogen-containing fluorine-hydrogen-containing carbon film as described above.
  • a simple metal, a metal compound for example, a metal oxide, a metal nitride, a metal carbide, ), Silicon alone, or a gas that forms one or more of silicon compounds (for example, silicon oxide, silicon nitride, silicon carbide).
  • a simple metal, metal compounds eg, metal oxides, metal nitrides, metal carbides
  • silicon alone e.g., silicon oxide, silicon
  • silicon compounds eg, silicon oxide, silicon
  • simple metals, metal compounds eg, metal oxides, metal nitrides, metal carbides
  • silicon simple substances silicon compounds (eg, silicon oxide, silicon nitride, silicon nitride)
  • Material, metal carbide), silicon simple substance, silicon compound for example, silicon oxide, silicon nitride, silicon carbide
  • a fluorine-containing carbon film may be formed.
  • the mixing ratio of the two gases with time the ratio of C-F bonds is continuously or gradually increased from the side closer to the substrate or the article in the thickness direction of the film.
  • a carbon film that changes so as to increase stepwise may be formed.
  • a fluorine-hydrogen-containing carbon film is formed by a plasma CVD method, various devices such as a parallel plate type plasma CVD device can be adopted.
  • a fluorine / hydrogen-containing carbon film may be formed as follows.
  • a film forming chamber including a plasma generating chamber and a plasma processing chamber connected to the plasma generating chamber is adopted as the film forming chamber, and the substrate for forming a carbon film or the article to be formed is installed in the plasma processing chamber.
  • a part of the film forming gas is introduced into the plasma processing chamber, and the rest is introduced into the plasma generating chamber.
  • the gas introduced into the chamber is turned into plasma under electric power supply, and the plasma is introduced into the plasma processing chamber to decompose the gas introduced into the plasma processing chamber (plasma ) Or
  • the gas introduced into the chamber is turned into plasma under electric power supply, and the gas introduced into the plasma processing chamber is turned into plasma under electric power supply.
  • a hydrogen-containing carbon film is formed.
  • the hydrocarbon compound gas and the carbon fluoride compound gas may be further used as a simple metal or a metal compound (for example, a metal acid).
  • silicon carbide, silicon nitride, and silicon compounds for example, silicon oxide, silicon nitride, and silicon carbide
  • a gas that forms one or more of a metal simple substance, a metal compound, a silicon simple substance, and a silicon compound is introduced into the plasma generation chamber. Then, the hydrocarbon compound gas and the carbon fluoride gas are introduced into the plasma processing chamber, and
  • the gas introduced into the chamber is turned into plasma under electric power supply, and the plasma is introduced into the plasma processing chamber to decompose the gas introduced into the plasma processing chamber (plasma ) Or
  • the gas introduced into the chamber is turned into plasma under electric power supply, and the gas introduced into the plasma processing chamber is also turned into plasma under electric power supply.
  • a fluorine-hydrogen-containing carbon film containing one or more of a metal simple substance, a metal compound, a silicon simple substance, and a silicon compound can be given.
  • the gas in the plasma generation chamber and the gas in the plasma processing chamber are used.
  • the gas plasma in the plasma generation chamber and the gas plasma in the plasma processing chamber can be controlled.
  • the following carbon film forming method can also be exemplified. That is, a film forming chamber including a plasma generating chamber and a plasma processing chamber connected to the plasma generating chamber is adopted as the film forming chamber, and the substrate for forming a carbon film or the article to be formed is installed in the plasma processing chamber.
  • the plasma generation chamber contains a simple metal, a metal compound (eg, a metal oxide, a metal nitride, a metal carbide), a simple silicon, a silicon compound (eg, a silicon oxide, A sputter target consisting of one or more of silicon nitride and silicon carbide), and introducing the hydrocarbon compound gas and the carbon fluoride compound gas into the plasma processing chamber; A sputtering gas is introduced into the plasma generation chamber, and the gas is supplied to the plasma generation chamber.
  • a metal compound eg, a metal oxide, a metal nitride, a metal carbide
  • a simple silicon eg, a silicon oxide, A sputter target consisting of one or more of silicon nitride and silicon carbide
  • the plasma and sputter particles generated by the sputtering of the sputter target under the plasma are introduced into the plasma processing chamber and introduced into the plasma processing chamber.
  • the hydrocarbon compound gas and the fluorocarbon compound gas are decomposed (plasmaized), or
  • examples of the sputtering gas include an inert gas (eg, argon gas).
  • the carbon film formed on the article by the method for producing a carbon film-coated article described above (hereinafter sometimes referred to as “hydrogen-nitrogen-containing carbon film”) is a carbon film having a C—N bond portion. is there. Therefore, not only the lubricating properties derived from the carbon film portion are provided, but also the hardness as a whole is increased due to the presence of the carbon film portion having a higher hardness than fluoride and the nitride portion having a higher hardness. There is excellent wear resistance.
  • the carbon film-coated article according to the above (2), coated with the hydrogen and nitrogen-containing carbon film, has high durability.
  • the hydrogen / nitrogen-containing carbon film according to the present invention may further include a simple substance of a metal, a metal compound (typically, a metal oxide, a metal nitride, and a metal carbide), and a silicon. Or one or more of silicon compounds (typically, silicon oxides, silicon nitrides, and silicon carbides).
  • a metal compound typically, a metal oxide, a metal nitride, and a metal carbide
  • silicon typically, silicon oxides, silicon nitrides, and silicon carbides.
  • the carbon film formed on an article by the method for manufacturing a carbon film-coated article described in (4) (3) and (4) (hereinafter, these may be referred to as “hydrogen / metal-containing carbon film”) is described below.
  • it has a high hardness carbon film portion, a simple metal, a metal compound (typically, a metal oxide, a metal nitride, a metal carbide), and a silicon.
  • the carbon film-coated article described in (3) in (2) above which is coated with such a carbon-containing film such as hydrogen and metal, has high durability.
  • the hydrogen / nitrogen-containing carbon film or the hydrogen / metal-containing carbon film according to the present invention may be any film having a predetermined hardness, but a typical example is a DLC (diamond-like carbon) film. it can.
  • the features of the DLC film are as described in relation to the fluorine-hydrogen-containing carbon film.
  • the hydrogen / nitrogen-containing carbon film or the hydrogen / metal-containing carbon film, and the method of forming the carbon film in the carbon film-coated article coated with any one of the above-described fluorine / hydrogen-containing carbon films As in the case of formation, a plasma CVD method, a sputtering method, an ion plating method and the like can be mentioned. The advantages of these film forming methods are as described above.
  • the method of forming a carbon film described in the above (3) (3) and (4) is used as a typical example of a method of manufacturing a carbon film-coated article.
  • the method described in (4) 3 ⁇ above using the method described in 3 ⁇ 4 of) can be cited. You.
  • the hydrocarbon compound gas that can be used for forming the carbon film in these methods is the same as the hydrocarbon compound gas that can be used in forming the fluorine-hydrogen-containing carbon film. If necessary, a mixture of such a hydrocarbon compound gas with a hydrogen gas, an inert gas, or the like as a carrier gas may be used.
  • nitrogen-containing gas a gas such as nitrogen (N 2 ), ammonia, or hydrazine can be used.
  • a hydrocarbon compound gas and a nitrogen-containing gas are used as a film-forming gas, and a simple metal or a metal compound (for example, a metal oxide) is used.
  • a simple metal or a metal compound for example, a metal oxide
  • a simple substance of a metal, a metal compound for example, a metal oxide, a metal nitride, or a metal carbide
  • a simple substance of silicon, a silicon compound for example, a silicon oxide,
  • a hydrogen / nitrogen-containing carbon film containing one or more of silicon nitride and silicon carbide may be formed.
  • silicon (S i) or metal oxides, nitrides, and carbides must be mixed into the film.
  • S i based compound Si H 4, TEOS or the like
  • T i compound [T i C
  • Oxygen and the like may be reacted with pentaethoxytitanium ((CH)), tetrasoproxititanium (T i (0—i-C) 4 ), and the like.
  • simple metals, metal compounds eg, metal oxides, metal nitrides, metal carbides
  • silicon simple substances silicon compounds (eg, silicon oxide, silicon nitride, silicon nitride)
  • metal element and metal compound eg, metal oxide, metal nitride, etc.
  • a hydrogen / nitrogen-containing carbon film or a hydrogen / metal-containing carbon film may be formed. «
  • various devices such as a parallel plate type plasma CVD device can be adopted, but for example, they may be formed as follows.
  • a film forming chamber including a plasma generating chamber and a plasma processing chamber connected to the plasma generating chamber is adopted as the film forming chamber, and the substrate for forming a carbon film or the article to be formed is placed in the plasma processing chamber. A part of the film-forming gas is introduced into the plasma processing chamber, and the rest is introduced into the plasma generation chamber; and
  • the gas introduced into the chamber is turned into plasma under electric power supply, and the plasma is introduced into the plasma processing chamber to decompose the gas introduced into the plasma processing chamber;
  • the gas introduced into the chamber is turned into plasma under power supply, and the gas introduced into the plasma processing chamber is turned into plasma under power supply.
  • a hydrogen / nitrogen-containing carbon film or a hydrogen / metal-containing carbon film is formed on the substrate or the article.
  • the hydrocarbon compound gas is introduced into the plasma processing chamber, and the nitrogen-containing gas is the plasma.
  • the nitrogen-containing gas is the plasma.
  • the nitrogen-containing gas introduced into the chamber is converted into a plasma under electric power supply, and the plasma is introduced into the plasma processing chamber, and the carbonization introduced into the plasma processing chamber is performed.
  • a hydrogen compound gas is decomposed (plasmaized) or b) the nitrogen-containing gas introduced into the plasma generation chamber is converted into a plasma under electric power supply, and the hydrocarbon introduced into the plasma processing chamber Compound gas is also turned into plasma under electric power supply,
  • the film-forming gas may include the hydrocarbon compound gas and the nitrogen-containing gas as well as a simple metal or a metal compound (for example, metal oxide, metal nitride, or the like). Or metal carbide), silicon simple substance, silicon compound (for example, silicon oxide, silicon nitride, silicon carbide)
  • a gas that forms one or more of a metal simple substance, a metal compound, a silicon simple substance, and a silicon compound is introduced into the plasma generation chamber. Introducing the hydrocarbon compound gas and the nitrogen-containing gas into the plasma processing chamber; and
  • the gas introduced into the chamber is turned into plasma, and the gas introduced into the plasma processing chamber is turned into plasma under electric power supply.
  • Examples of forming a hydrogen / nitrogen-containing carbon film containing one or more of a metal compound, a simple substance of silicon, and a silicon compound can be given.
  • the following carbon film forming method can also be exemplified. That is, a film forming chamber including a plasma generating chamber and a plasma processing chamber connected to the plasma generating chamber is adopted as the film forming chamber, and the substrate for forming a carbon film or the article to be formed is installed in the plasma processing chamber.
  • the plasma generation chamber contains a simple metal, a metal compound (eg, a metal oxide, a metal nitride, a metal carbide), a silicon simple substance, a silicon compound (eg, a silicon oxide, a silicon oxide).
  • a sputter target consisting of one or more of nitrogen nitride and silicon carbide), and the hydrocarbon compound gas and the nitrogen-containing gas are introduced into the plasma processing chamber.
  • a gas for snow and sputtering is introduced into the plasma generation chamber to convert the gas into a plasma under electric power supply, and the plasma and the sputtering target are sputtered under the plasma.
  • the sputter particles generated by the blasting are introduced into the plasma processing chamber, and the hydrocarbon compound gas and the nitrogen-containing gas introduced into the plasma processing chamber are decomposed (plasmaized), or
  • a gas for sputtering is introduced into the plasma generation chamber to convert the gas into a plasma under electric power supply, and the sputtering target is sputtered based on the plasma.
  • the hydrocarbon compound gas and the nitrogen-containing gas introduced into the plasma processing chamber are also introduced. It's turned into a plasma under power supply,
  • examples of the sputtering gas include an inert gas (eg, argon gas).
  • a film formation chamber including a plasma generation chamber and a plasma processing chamber connected to the plasma generation chamber is adopted as the film formation chamber.
  • the substrate or the article to be coated is placed in the plasma processing chamber, and for a gas forming one or more of a simple metal, a metal compound, a single silicon, and a silicon compound, the plasma generating chamber is used.
  • the hydrocarbon compound gas is introduced into the plasma processing chamber, and
  • the gas introduced into the chamber is turned into plasma under electric power supply, and the plasma is introduced into the plasma processing chamber, and the hydrocarbon compound gas introduced into the plasma processing chamber is discharged. Decomposes (converts into plasma) or b) converts the gas introduced into the plasma generation chamber into plasma under power supply, and also converts the gas introduced into the plasma processing chamber under power supply into plasma.
  • a method of forming a carbon film containing hydrogen and one or two or more of a metal simple substance, a metal compound, a silicon simple substance, and a silicon compound on the substrate can also be exemplified.
  • any of the above-mentioned fluorine / hydrogen-containing carbon film, hydrogen / nitrogen-containing carbon film, hydrogen / metal-containing carbon film, both DC power and high frequency power are used as the gas plasma power.
  • high-frequency power high-frequency power obtained by subjecting basic high-frequency power of a predetermined frequency to amplitude modulation at a predetermined modulation frequency may be employed.
  • the fundamental high-frequency power of a predetermined frequency (for example, 13.56 MHz) is oscillated at a modulation frequency in the range of 1/10000 to 1/10 of the predetermined frequency.
  • An example is the use of high-frequency power in a state where width modulation has been performed.
  • a high-density plasma can be obtained, thereby improving the reaction rate.
  • the film can be formed at a low temperature.
  • the reaction on the outer surface of the substrate for film formation or the outer surface of the article to be formed proceeds, and the film adhesion can be improved.
  • the film speed can be improved. This can improve productivity.
  • the waveform of the basic high-frequency power before modulation may be any of a sinusoidal wave, a square wave, a sawtooth wave, a triangular wave, and the like.
  • the amplitude modulation may be a pulse modulation by turning on / off a power supply, and may be a pulse-like modulation.
  • the basic high-frequency power is not limited, but may be a power of 13.56 MHz or more. This is because if the diameter becomes smaller, the plasma density tends to be insufficient. Further, the frequency of the basic high-frequency power may be set to, for example, about 500 MHz from the high-frequency power supply cost.
  • the reason why the modulation frequency in the above range is used is that the deposition rate is reduced when the modulation frequency becomes lower than 1 / 100,000 of the frequency of the basic high frequency power. On the other hand, if it is larger than 1/10, matching becomes difficult, and the film thickness uniformity is reduced.
  • the modulation duty ratio (on time / on time + off time) may be set to about 5% to 90%.
  • the film formation rate decreases when the concentration is smaller than 5%, and the power supply time is too long when the ratio is larger than 90%. This is because there is less.
  • any of a fluorine-hydrogen-containing carbon film, a hydrogen-nitrogen-containing carbon film, and a hydrogen-metal-containing carbon film may be subjected to the above-described substrate or film-forming article as a pretreatment prior to the formation of the carbon film.
  • the film formation surface may be exposed to plasma of at least one of a fluorine-containing gas, a hydrogen gas, and an oxygen gas.
  • fluorine-containing gas examples include fluorine (F 2 ) gas, nitrogen trifluoride (NF 3 ) gas, sulfur hexafluoride (SF 6 ) gas, carbon tetrafluoride (CF 4 ) gas, Carbon difluoride (C 2 F) gas, tetrafluorocarbon 8 (C 4 F 8 ) gas, i F) gas, hexafluoride 2 Geimoto (S i 2 F 6) gas, 3 chlorine fluoride (C 1 F 3) gas, it is a this include full Tsu hydrogen (HF) gas or the like.
  • fluorine (F 2 ) gas nitrogen trifluoride (NF 3 ) gas
  • sulfur hexafluoride (SF 6 ) gas sulfur hexafluoride
  • CF 4 carbon tetrafluoride
  • C 2 F Carbon difluoride
  • C 4 F 8 tetrafluorocarbon 8
  • i F hexafluoride 2 Geimoto
  • the film-forming surface of the film-forming substrate or the film-forming article By exposing the film-forming surface of the film-forming substrate or the film-forming article to the plasma of the pretreatment gas, the film-forming surface is cleaned or the surface roughness of the film-forming surface is further improved. The degree improves. These contribute to the improvement of the adhesion of the carbon film, and a highly adherent carbon film can be obtained.
  • the film-forming substrate or the film-forming surface of the film-forming article is made of an organic material such as rubber or resin
  • the fluorine-containing gas plasma when the fluorine-containing gas plasma is used, the film-forming surface is thereby blown.
  • hydrogen gas plasma When hydrogen gas plasma is employed, the surface to be deposited is terminated with hydrogen.
  • the pretreatment with plasma may be performed a plurality of times using the same type of plasma or using different types of plasma. For example, when a deposition surface is exposed to an oxygen gas plasma and then to a fluorine-containing gas plasma or a hydrogen gas plasma and a carbon film is formed thereon, the deposition surface is cleaned. After that, the surface is terminated with fluorine or hydrogen, and the adhesion between the carbon film formed thereafter and the surface on which the film is to be formed becomes very good.
  • At least the surface coated with the carbon film may be formed of rubber and / or resin, At least the surface covered with the carbon film may be formed of metal and / or ceramic.
  • Such rubbers include natural rubber, butyl rubber, ethylene propylene rubber, black rubber, chlorinated polyethylene rubber, epichlorohydrin rubber, acryl rubber, nitrile rubber, urethane rubber, silicone rubber, Examples include fluoro rubber
  • a thermosetting resin or a thermoplastic resin can be used.
  • the thermosetting resin include a phenol-formaldehyde resin, a urea resin, and a melamine-formaldehyde resin.
  • Thermoplastic resins include vinyl resins (polyvinyl chloride, polyvinyl butylate, polyvinyl alcohol, polyvinyl acetate, polyvinyl formal, poly (vinyl chloride), etc.), polyvinylidene chloride, chlorinated polyether, and poly (vinyl chloride).
  • Ester resin polystyrene, styrene-acrylonitrile copolymer, etc.
  • ABS polyethylene
  • polypropylene polyacetal
  • acrylic resin polymer Chilmethacrylate, modified acrylic, etc.
  • polyamide resin Nylon 6, 66, 61, 11 etc.
  • cellulose resin ethyl cellulose, cellulose acetate, etc.
  • Propylcellulose cellulose acetate butyrate, cellulose nitrate, etc.
  • polycarbonate epoxy resin
  • fluorine resin ethylene trifluoride
  • Resin such as polyethylene, ethylene tetrafluoride, ethylene tetrafluoride, propylene fluoride, and vinylidene fluoride
  • polyurethane polyurethane.
  • Examples of the metal include hard metal carbides such as stainless steel and WC, high-speed steel (high-speed steel), aluminum, and aluminum alloys.
  • Examples of the ceramic include aluminum, Examples thereof include silicon nitride, aluminum nitride, and silicon nitride.
  • the article in the carbon film-coated article according to the present invention is not particularly limited. Any material can be used as long as it can form the carbon film according to the present invention. Any article, including the following, can be a target of the carbon film formation of the present invention.
  • FIG. 1 is a diagram showing a schematic configuration of an example of a film forming apparatus that can be used for forming a carbon film and manufacturing a carbon film-coated article according to the present invention.
  • the apparatus shown in FIG. 1 is a plasma CVD apparatus, which has a vacuum chamber 1 (an example of a film forming chamber) to which an exhaust pump 12 is connected via a pressure regulating valve 11. Electrode 2 and electrode 3 are installed at the position opposite to electrode 2. The electrode 3 is grounded, and the electrode 2 is connected to a high-frequency power supply 13 via a matching box 22. In addition, the electrode 2 is provided with a heater 21 for heating the article S to be deposited thereon, which is supported thereon, to a deposition temperature.
  • the chamber 1 is provided with a gas supply unit 4 so that a film forming gas can be introduced into the chamber 1.
  • the gas supply unit 4 is provided with one or more film-forming gases connected via mass flow controllers 41 1, 41 2 ′ and valves 42 1, 42 2 ′. Gas sources 431, 4332 ⁇ ⁇ ⁇ are included.
  • a film-forming article (here, a rubber plate for vibration isolation) S of a predetermined material is placed on the high-frequency electrode 2 in the chamber 1 with its film-forming surface facing the electrode 3, and the air is exhausted. Reduce the pressure inside chamber 1 to the specified pressure by operating pump 12.
  • at least one of fluorine-containing gas, hydrogen gas and oxygen gas is introduced into the chamber 1 from the gas supply unit 4 as a pretreatment gas, and a high-frequency power supply 23 is used to supply a matching box.
  • Cousin High-frequency power is supplied to the electrode 2 via 22, whereby the introduced pretreatment gas is made into a plasma, and the film-forming surface S 1 of the article S is pretreated under the plasma. It is desirable to perform this surface treatment (pretreatment), but it is not always necessary.
  • the inside of the chamber 1 is evacuated again, the pressure is readjusted, and a film forming gas is introduced from the gas supply unit 4 into the chamber 1.
  • the film forming gas includes a hydrocarbon compound gas and a gas containing a carbon fluoride compound gas when forming a fluorine-containing or hydrogen-containing carbon film, and a hydrocarbon compound gas when forming a hydrogen-nitrogen-containing carbon film.
  • a hydrocarbon compound gas and a metal alone, a metal compound, a silicon alone, or a silicon compound may be used.
  • a high-frequency power is supplied to the electrode 2 from the high-frequency power source 23 via the matching box 22 by introducing a gas containing a gas forming one or more than two, whereby the introduced gas is converted into a plasma.
  • a carbon film 5 is formed on the film-forming surface S 1 of the material S under the plasma.
  • a gas containing a hydrocarbon compound gas and a fluorocarbon compound gas is used as a film-forming gas.
  • a fluorine-containing hydrogen-containing carbon film is used and a gas containing a hydrocarbon compound gas and a nitrogen-containing gas is used, the film becomes a hydrogen-nitrogen-containing carbon film, and the hydrocarbon compound gas and a single metal, a metal compound, and a silicon compound are used.
  • a gas containing a gas that forms one or more of silicon alone and a silicon compound is used, a carbon film containing hydrogen, metal, or the like is obtained.
  • the hydrocarbon compound gas and the fluorocarbon compound gas are introduced into the vacuum chamber 1.
  • the carbon film 5 obtained by adjusting the mixture ratio (introduction flow rate ratio) of both gases is derived from C—F bonds in the spectrum by FT-IR (Fourier transform infrared) spectroscopy.
  • This carbon film has the characteristics of the DLC film described above, is formed with good adhesion to the article S, has sufficient hardness, has excellent wear resistance, and contains a C-F bond. Therefore, the slidability or lubricity with other articles is good.
  • This carbon film has the characteristics of the DLC film described above, is formed with good adhesion to the article S, has sufficient hardness, has excellent wear resistance, and has lubricity derived from the DLC film portion. And high hardness due to the presence of the DLC film portion and the C—N bond portion.
  • the case of forming a carbon film containing hydrogen, metal, etc. will be further described.
  • the hydrocarbon compound gas and the metal alone, the metal compound, the silicon alone, and the silicon are used.
  • the mixing ratio (introduction flow ratio) of the two gases is adjusted so that the carbon film (such as a metal film) in which such metals and the like are dispersed is formed. DLC film in the example).
  • This carbon film has the characteristics of the DLC film described above, is formed with good adhesion to the article S, has sufficient hardness, has excellent wear resistance, and has lubricity derived from the DLC film portion. It has high hardness due to the presence of the DLC film portion and the portion such as metal.
  • the film forming apparatus shown in FIG. 2 is also a plasma CVD apparatus. This device is obtained by connecting an arbitrary waveform generator 24 to a high-frequency power source 23 in the device shown in FIG.
  • the other points are the same as those of the apparatus shown in FIG. 1, and the same parts as those of the apparatus shown in FIG. 1 are denoted by the same reference numerals.
  • the pulse-modulated high-frequency power generated by the high-frequency power source 23 and the arbitrary waveform generator 24 is passed through the matching box 22.
  • the gas for film formation is turned into plasma by supplying to the internal electrode 2.
  • the pulse-modulated high-frequency power is obtained by modulating a basic high-frequency power having a predetermined frequency of 13.56 MHz or more with a modulation frequency in a range of 1 / 100,000 to 1/10 of the predetermined frequency. State.
  • the duty ratio (ON time / ON time + OFF time) should be 10% to 90%.
  • Other operations are the same as the film formation using the apparatus shown in FIG.
  • a carbon-coated article similar to that in the apparatus in FIG. 1 can be obtained by film formation using the apparatus in FIG. 2, but the electric power supplied for plasma-forming the film-forming gas is as described above.
  • high-frequency power subjected to pulse modulation high-density plasma can be obtained, thereby improving the reaction rate and forming a film at a low temperature.
  • a reaction on the surface of the article proceeds, so that the film adhesion can be improved and the film forming speed can be improved.
  • the plasma CVD apparatus shown in FIG. 3 can also be used for forming a carbon film and manufacturing a carbon film-coated article according to the present invention.
  • the plasma CVD apparatus shown in FIG. 3 includes a cylinder-type plasma generation chamber 10 and a cylinder-type plasma processing chamber 10. These form a vacuum chamber R (an example of a deposition chamber). Both chambers 10 and 20 are vertically connected with the same central axis.
  • the plasma generation chamber 10 is provided with an RF coil 110 in the form of an antenna along its outer peripheral wall, and the antenna 110 has a 13.56 MHz through a matching box 130.
  • the high frequency power supply (RF power supply) 140 of z is connected.
  • the plasma processing chamber 20 is provided with a holder 200 that supports a film-forming article S disposed at a lower portion of the chamber, and an exhaust device 100 is provided below the holder 200.
  • a gas introduction pipe 150 is connected to the plasma generation chamber 10, and a gas supply unit (not shown) is connected to the gas introduction pipe 150.
  • a gas inlet pipe 30 is inserted and installed at a position slightly below the boundary between the plasma generation chamber 10 and the plasma processing chamber 20, and an endless ring-shaped gas ejection pipe 30 is inserted into the inlet pipe.
  • 0 is connected to the gas introduction pipe 30, and another gas supply unit (not shown) is connected outside the room.
  • the gas ejection pipe 300 is arranged at a position facing the article S, and has a large number of gas ejection holes directed toward the holder 200 at equal intervals. T / JP00 / 03886
  • the holder 200 is water-cooled by circulating cooling water using a water-cooling pipe 201 as necessary, or is heated by a heater H built in the holder.
  • a high frequency power supply (RF power supply) 420 is connected to the holder 200 via a matching box 410, and a DC power supply 4300 or 4400 is further connected thereto.
  • the switching switch SW can switch and connect the power supply 430 or 440 to the holder 200 as required.
  • the incident plasma is controlled by the DC power supply 430 or 440 to perform high-speed film formation.
  • Membranes are possible.
  • high-speed film formation is possible by applying a high-frequency power source 420.
  • the high-frequency power supplies 140 and 420 are connected via a phase shifter 500.
  • a part of the film forming gas for forming the carbon film is plasma.
  • the remaining gas is introduced into the processing chamber 20 and the rest is introduced into the plasma generation chamber 10, and the gas introduced into the plasma generation chamber 10 is fed from the high-frequency power supply 140 to the antenna 110.
  • a plasma is generated by forming a high-frequency induction electric field by supplying a high-frequency power to the plasma, and the plasma is introduced into the plasma processing chamber 20.
  • the plasma supplied to the plasma processing chamber 20 decomposes the gas in the plasma processing chamber 20 to form a carbon film on the article S.
  • the gas in the plasma processing chamber 20 may be positively decomposed (plasmaized). This makes it possible to control the gas plasma generation in the plasma generation chamber 10 and the gas plasma generation in the plasma processing chamber 20 respectively.
  • the carbon film when manufacturing a carbon film or a carbon film-coated article using any of the film forming apparatuses shown in FIGS. 1 to 3, when the carbon film is a fluorine-hydrogen-containing carbon film, the carbon film must have higher hardness. Is required, in forming the carbon film, a nitrogen-containing gas is used as the film-forming gas in addition to the hydrocarbon compound gas and the carbon fluoride compound gas. Gas into chamber 1 or R. As a result, a carbon film containing nitrogen, in addition to fluorine and hydrogen, and having higher hardness is formed. Is done.
  • a simple substance of a metal, a metal compound for example, a metal oxide, a metal nitride, or a metal carbide
  • a simple substance of silicon for example, a silicon compound
  • a silicon compound for example, a silicon oxide
  • a gas that forms the desired one or more of silicon nitride and silicon carbide is introduced into chamber 1 or R, thereby adding fluorine and hydrogen
  • Metal, metal compounds eg, metal oxides, metal nitrides, metal carbides
  • a gas that forms one or more of a metal simple substance, a metal compound, a silicon simple substance, and a silicon compound as described above may be used.
  • the apparatus shown in Fig. 3 was used, and the gas was introduced into the plasma generation chamber 10 and the hydrocarbon compound gas and the carbon fluoride compound gas were introduced into the plasma processing chamber 20. can do.
  • the plasma directly involved in the formation of the carbon film and the plasma involved in the doping of a metal or the like can be controlled separately, so that the doping amount of the metal or the like can be controlled and the film quality can be controlled.
  • the control of can be performed independently.
  • a carbon film or a carbon film-coated article is manufactured by any of the film forming apparatuses shown in FIGS. 1 to 3, when the carbon film is a hydrogen / nitrogen-containing carbon film, the carbon film is higher.
  • a metal compound for example, a metal oxide, a metal nitride, or a metal carbide
  • a silicon simple substance for example, a silicon compound (for example, A gas that forms one or more of the desired silicon oxide, silicon nitride, silicon carbide) is introduced into chamber 1 or R, thereby adding hydrogen and nitrogen.
  • a carbon film containing one or more of the above and having a higher hardness can be formed.
  • a gas that forms one or more of a metal simple substance, a metal compound, a silicon simple substance, and a silicon compound is used as a film forming gas as shown in FIG.
  • An apparatus is employed, and the gas can be introduced into the plasma generation chamber i 0, and the hydrocarbon compound gas and the nitrogen-containing gas can be introduced into the plasma processing chamber 20. This makes it easier to control the film quality.
  • a gas for forming a metal or the like is introduced into the plasma generation chamber 10 and a hydrocarbon compound gas is introduced into the plasma processing chamber 20. Can be introduced.
  • a nitrogen-containing gas may be introduced into the plasma generation chamber 10 and a carbon hydride compound gas may be introduced into the plasma processing chamber 20.
  • the plasma CVD apparatus shown in FIG. 14 (A) can also be used for forming a carbon film and manufacturing a carbon film-coated article according to the present invention.
  • a sputter target 600 is arranged in the plasma generation chamber 10 in the plasma CVD apparatus shown in FIG. 3, and the target sputtering is performed in the target 600.
  • a bias DC power supply 700 for the power supply for the power supply.
  • the antenna 110 shown in FIG. 14 (A) the plasma generation chamber 10 shown in FIG. 14 (B) was used as an electrode for converting the gas in the plasma generation chamber into plasma.
  • a high-frequency electrode 111 and a ground electrode 112, etc. installed outside the antenna may be used.
  • the sputtering target used in the film forming apparatus shown in FIG. 14 is made of a doped material capable of improving the film hardness, such as a simple metal, a metal compound (eg, a metal oxide, a metal nitride). , Metal carbides), silicon alone, or silicon compounds (for example, silicon oxide, silicon nitride, silicon carbide) Sputters, titanium, silicon, carbon, aluminum, copper, iron, chromium, titanium nitride, boron nitride, chromium nitride, titanium oxide, etc. Can be mentioned.
  • a doped material capable of improving the film hardness such as a simple metal, a metal compound (eg, a metal oxide, a metal nitride).
  • Metal carbides e.g, Metal carbides
  • silicon alone e.g., silicon oxide, silicon nitride, silicon carbide
  • silicon compounds for example, silicon oxide, silicon nitride, silicon carbide
  • the hydrocarbon compound gas and the carbon fluoride compound gas are introduced into the plasma processing chamber 20.
  • a hydrocarbon compound gas Nitrogen-containing gas is introduced into the plasma processing chamber 20, and when a carbon film containing hydrogen, metal, etc. is formed, hydrocarbon compound gas is introduced into the plasma processing chamber 20, and in any case, plasma is generated.
  • a sputtering gas consisting of an inert gas or the like is introduced into the chamber 10, and the gas for the sputtering is supplied by high-frequency power supply to the antenna 110 from the high-frequency power supply 140.
  • a plasma is formed by the formation of a high-frequency induction electric field (or a high-frequency power is applied from the high-frequency power supply 140 to the high-frequency electrode 111 to form a plasma), and the plasma thus generated and the source of the plasma are generated.
  • Sputter particles generated by sputtering of the sputtering target 600 are introduced into the plasma processing chamber 20 and a hydrocarbon compound gas and a fluorocarbon compound gas, or a hydrocarbon compound gas are introduced.
  • a nitrogen-containing gas or hydrocarbon compound gas to form a carbon film on the article S containing one or more of a metal alone, a metal compound, a silicon alone, and a silicon compound It is possible to do so.
  • high-frequency power may be applied to the holder 200 from a power supply 420 having an appropriate output to actively decompose (plasma) the gas in the plasma processing chamber 20.
  • a nitrogen-containing gas may be added to the film-forming gas also in the apparatus shown in FIG.
  • a hydrocarbon compound gas introduced into chamber 1 or R is used.
  • the mixing ratio (introduction flow ratio) of the fluorocarbon compound gas over time the ratio of C-F bonds from the side closer to the surface of the article S to the side farther from the surface of the article S in the thickness direction of the film is increased.
  • a carbon film that changes so as to increase continuously or stepwise may be formed.
  • Such a carbon film as a whole has high hardness, good slidability or lubricity, and good adhesion to a film-formed article.
  • Pretreatment was performed, and then a DLC film was formed on the treated surface (Experimental Examples X-2 to X-5), and the adhesion and the like of these DLC films were evaluated.
  • All materials to be coated were made of EPDM (ethylene propylene rubber) and sized 20 cm in diameter x 1 Omm in thickness. The electrode size of the device was 40 cm x 40 cm (square).
  • Source gas for film formation Methane (CH 4 ) gas lOOsccm High frequency power frequency 13.56 MHz, 300 W
  • the article Prior to the formation of the DLC film, the article was subjected to a pretreatment with hydrogen gas plasma under the following conditions, and then the pretreatment gas was exhausted, and then a DLC film was formed.
  • the deposition conditions were the same as in Experimental Example X-1.
  • the article Prior to the formation of the DLC film, the article was subjected to a pretreatment with a fluorine compound gas plasma under the following conditions, and then the pretreatment gas was evacuated to form a DLC film.
  • the deposition conditions were the same as in Experimental Example X-1. -Pretreatment conditions
  • Pretreatment gas sulfur hexafluoride (SF 6), l OO sccm RF power 1 3. 5 6 MH z, 3 0 0 W
  • the article Prior to the formation of the DLC film, the article was subjected to a first pretreatment with oxygen gas plasma under the following conditions, a second pretreatment with hydrogen gas plasma, and then exhausting the pretreatment gas.
  • a DLC film was formed.
  • the film forming conditions were the same as in Example X-1.
  • the article Prior to the formation of the DLC film, the article was subjected to a first pretreatment with oxygen gas plasma under the following conditions, a second pretreatment with a fluorine compound gas plasma, and then the pretreatment gas was exhausted. After that, a DLC film was formed.
  • the film formation conditions were the same as in Experimental Example (1-1).
  • Pretreatment gas Sulfur hexafluoride (SF 6 ), 100 sccm High frequency power 13.56 MHz, 300 W
  • the film adhesion is improved by performing the plasma pretreatment on the article surface prior to the formation of the DLC film.
  • the wear resistance is improved by coating the DLC film, and the wear resistance is further improved by performing the pretreatment.
  • the article coated with the DLC film formed by the pretreatment has about 9 times higher abrasion resistance than the article without the DLC film coating.
  • Source gas for film formation Methane (CH 4 ) gas lOOsccm High frequency power frequency 13.56 MHz, 300 W
  • Source gas for film formation Benzene (C 6 H) gas 20 sccm High frequency power Frequency 13.56 MHz, 300 W
  • the coefficient of friction was measured using a pin-on-disk friction and wear tester, with a load of 50 g, a radius of gyration of 5 mm, and a linear velocity of 10 cm / sec for 1 hour. was defined as the friction coefficient.
  • Abrasion resistance was measured by measuring the depth from the film surface to the bottom of the wear mark with a step gauge after the friction coefficient measurement test using the pin-on-disk type friction and wear tester described above. , evaluated.
  • the film adhesion was evaluated by a cross-cut method of a tape separation test (JISK540-190).
  • Hardness was measured with a micro hardness tester at a load of 5 mg and a displacement of 0 1 m.
  • the carbon number is higher than that of methane gas. It is considered that the improvement in the friction and wear characteristics is due to the fact that the hydrogen concentration contained in the film was reduced and the film hardness was improved.
  • Pretreatment gas hydrogen (H 2) gas 1 0 0 sccm
  • Film formation The film was formed after exhausting the pretreatment gas.
  • the amount of gas introduced was kept constant at 25 sccm for carbon difluoride and gas as shown in Figure 5 and Table 1 below for methane gas in order to change the proportion of fluorine added. I let it.
  • the mixing ratio of both of them (introduction flow rate ratio) and (Ji 2? 6) / (Ji ⁇ ⁇ + Ji 2? 6).
  • the flow ratios are 0.2 for Experimental Examples 1-1, 0.33 for Experimental Examples 1-1, 0.5 for Experimental Examples 1-3, 0.71 for Experimental Examples 1-4, and 0.83 for Experimental Examples 115.
  • Figure 5 shows the change in deposition rate when the flow ratio is changed. From Fig. 5, it can be seen that the film formation rate can be increased up to three times by mixing the fluorocarbon compound gas. However, as the flow ratio becomes 1, the deposition rate decreases, and near 1 the article is etched. Therefore, it is preferable that the film is formed at a flow rate ratio of 0.9 or less. Generally speaking, from the viewpoint of the deposition rate, it is preferable that the flow rate ratio [fluorocarbon compound gas / (hydrocarbon compound gas + carbon fluoride compound gas)] be 0.9 or less. New
  • Fig. 9 shows the relationship between the friction coefficient and the carbon films of Experimental Examples 1-1 to 115 and Comparative Experimental Example 1.
  • the friction coefficient was measured using a reciprocating sliding friction and wear tester.
  • the load was measured by reciprocating 10 times at 10 g.
  • the flow ratio should be around 0.5, which does not exceed 0.7, in order to improve lubricity.
  • the flow rate ratio fluorocarbon compound gas / (hydrocarbon compound gas + carbon compound gas)
  • FIG. 10 shows the evaluation results of the hardness (Vickers hardness) of the carbon films of Experimental Examples 1-1 to 1-15 and Comparative Example 1.
  • the film hardness was measured with a microhardness tester under a load of 10 mg and a displacement of 0.25 ⁇ m.
  • Flow rate ratio from FIG. [(C 2 F) / (CH 4 + C 2 T ⁇ ⁇ 6
  • the film hardness decreases, especially when the flow ratio is 0.7 or more. Therefore, when a hardness equivalent to that of the carbon film is required, a flow rate ratio of 0.5 or less is desirable.
  • the flow ratio [carbon fluoride gas / (hydrocarbon compound gas + carbon fluoride gas)] should be 0.5 or less. Desirable.
  • the water repellency of the carbon films of Experimental Examples 11 to 11 and Comparative Example 1 was evaluated.
  • the water repellency was evaluated by placing a water drop of pure water on each carbon film and measuring the contact angle.
  • the contact angle is the angle between the tangent drawn to the liquid at the three-phase contact point of the solid, liquid, and gas and the angle between the solid surface and the liquid. The larger the corner, the better the water repellency.
  • Figure 1 1 shows the relationship between our Keru flow ratio in each carbon films [(C 2 F 6) / ( CH 4 + C 2 F 6) ] and the contact angle (water repellent). As shown in FIG. 11, the water repellency increases as the flow ratio increases.
  • the flow rate ratio is desirably 0.7 or more.
  • the flow ratio [fluorocarbon compound gas / (hydrocarbon compound gas + carbon compound gas)] be 0.7 or more.
  • Table 1 summarizes the evaluation results described above.
  • Film formation The film was formed after exhausting the pretreatment gas.
  • Deposition gas Methan (C) gas Methan (C) gas
  • the amount of gas introduced was kept constant at 25 sccm for carbon difluoride and carbon dioxide, and changed as shown in Table 2 below for methane gas in order to change the proportion of fluorine added stepwise. I let it.
  • the hardness of the film can be increased to about 1.2 times to about 2.5 times by introducing nitrogen gas. It is thought that nitride was formed on the film
  • TE ⁇ S and oxygen gas are adopted as the deposition gas, and methane (CH 4 ) gas is introduced into the plasma processing chamber 10.
  • methane (CH 4 ) gas is introduced into the plasma processing chamber 10.
  • TEOS and oxygen gas are introduced into the plasma generation chamber 10 to form a carbon film, and Reference Experimental Example 411 is also shown.
  • Pretreatment Hydrogen gas for pretreatment was introduced into the deposition chamber R.
  • Pretreatment was performed under the same conditions as in the pretreatment in 1-5.
  • Deposition gas Pre-treatment gas was exhausted, and then deposition was performed.
  • Deposition gas methane (CH 4 ) gas and carbon difluoride (C 2 F 6) gas (25 sccm) Introduce to
  • the hardness of these carbon films was evaluated.
  • the hardness evaluation method is the same as that in the above-described Experimental Examples 11-11 to 115.
  • the evaluation results are shown in Table 5 below.
  • the addition of silicon oxide to the carbon film increases the film hardness to about 2 to 4 times, and is about 2 times less than that when nitrogen is mixed as described above. It can be seen that
  • the power for gas plasma is selected independently of each other, and this can be efficiently decomposed with appropriate power according to each gas. I understand.
  • the improvement of the film hardness was achieved by using a metal alone, a metal compound, a silicon alone, or other silicon. This can also be achieved by adding a compound.
  • the raw materials that can be used for these additions, the raw materials used in combination (raw material 1 and raw material 2), and examples of the added materials generated in the carbon film by this are summarized in Table 6 below. Table 6 classifies silicon alone as metal and silicon compound as metal compound.
  • Experimental Example 5 1 to 5 — 3 and Comparative Experimental Example 5 — Flow Ratio for Each of C-(N 2 ) / (N + CH 6 ), Film Deposition Rate, Coefficient of Friction, Wear Depth, Film Hardness, Tape Table 7 shows the separation test results. The friction coefficient, abrasion depth, film hardness, and tape separation test were evaluated in the same manner as the evaluation methods described in Experimental Examples II and Y-2.
  • the friction coefficient can be suppressed up to 60%, but when the nitrogen flow ratio exceeds 0.5, the friction coefficient increases. Therefore, from the viewpoint of the coefficient of friction, the flow rate ratio is preferably 0.5 or less.
  • the addition of nitrogen reduces the wear depth, but when the nitrogen flow ratio exceeds 0.5, the wear depth tends to increase. Therefore, from the viewpoint of wear depth, the flow rate ratio is preferably 0.5 or less.
  • the addition of nitrogen increases the film hardness, but when the flow rate ratio exceeds 0.5, the film hardness is lower than when no nitrogen is added. From the viewpoint of hardness, the flow rate ratio is preferably 0.5 or less.
  • the flow rate ratio is preferably 0.5 or less.
  • the deposition rate decreases as the amount of ⁇ 0S introduced increases.
  • the coefficient of friction decreases as the amount of ⁇ ⁇ 0 S introduced increases.
  • the wear depth also decreases as the amount of S ⁇ 0 S introduced increases.
  • the film hardness decreases by 0% when the amount of S ⁇ S introduced becomes 30 sccm.
  • the film adhesion decreases as the amount of TEOS introduced becomes 30 sccm. Based on these facts, it can be said that the TEOS introduction amount is preferably 20 sccm or less.
  • a high-frequency electrode 111 and a ground electrode 111 as shown in FIG. 14B are employed instead of the RF antenna 110 in the plasma generation chamber 10, and a phase shifter 50 is used.
  • An experimental example (Experimental example 7-1) of manufacturing a carbon film-coated article containing hydrogen and a metal oxide using the film-forming apparatus from which 0 was removed will be described.
  • All of the film-deposited products are made of silicone rubber and have a size of 20 cm in diameter and a thickness of 1 4 9 JP00 / 03886 mm.
  • the electrode (holder 200) size of the device was 40 cm x 40 cm (square).
  • Example 7 1, Comparative example 5 — C as described above, and Example 6 — 2 with the apparatus shown in Fig. 1 as described above-Film deposition rate, friction coefficient, wear depth, film hardness, tape separation test
  • Table 9 shows the results. The friction coefficient, abrasion depth, film hardness, and tape separation test were evaluated by the same methods as those described in Experimental Examples II-1 and II-2. Table 9
  • the use of the film forming apparatus in which the film forming chamber R is divided into the plasma generating chamber 10 and the plasma processing chamber 10 is more effective than the case of using the film forming apparatus shown in FIG. It can be seen that the film speed increased, the coefficient of friction and the wear depth decreased, and the film hardness improved.
  • gas plasma power is selected, and gas can be efficiently decomposed with an appropriate power corresponding to each gas.
  • the improvement of the film hardness can also be achieved by adding a simple metal or a metal compound other than silicon oxide.
  • the raw materials that can be used for these additions, the raw materials used in combination, and examples of the added materials generated in the carbon film by this are summarized in Table 6 described above. If not introduced simultaneously with the reaction gas, pure metal can be added.
  • the carbon film according to the present invention By forming the carbon film according to the present invention on an article such as a machine part, its hardness, lubricity and wear resistance can be improved.
  • the carbon film according to the present invention can be applied to an article requiring one or more of hardness, lubricity and abrasion resistance. Further, according to the method for forming a carbon film according to the present invention, such a carbon film is formed into an article with good adhesion. Can be achieved.

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Abstract

L'invention concerne un film de carbone contenant du fluor et de l'hydrogène et possédant, d'une part, dans un spectre obtenu par spectroscopie infrarouge à transformée de Fourier (FT-IR), un rapport (IR . C-F)/(IR . C-H) entre la zone (IR . C-F) d'une crête de l'ordre de 1000 à 1300 cm-1 attribuée à une liaison C-F et la zone (IR .C-H) d'une crête de l'ordre de 2800 à 3100 cm-1 attribuée à une liaison C-H de valeur supérieure à 0, et, d'autre part, dans un spectre obtenu par spectroscopie de photoélectrons XPS, un rapport (F¿1S? / C1S) entre l'intensité d'une crête attribuée à F1 et l'intensité d'une crête attribuée à C1S, d'une valeur supérieure à 0 et inférieure à 3. L'invention concerne encore un film de carbone contenant de l'hydrogène et de l'azote, ainsi qu'un film de carbone contenant de l'hydrogène et au moins un élément choisi dans le groupe constitué par un métal, un composé métallique, du silicium et un composé de silicium.
PCT/JP2000/003886 1999-06-18 2000-06-14 Film de carbone, procede de formation associe, article recouvert de ce film, et procede de preparation de cet article WO2000079020A1 (fr)

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US09/744,985 US6652969B1 (en) 1999-06-18 2000-06-14 Carbon film method for formation thereof and article covered with carbon film and method for preparation thereof
EP00939067A EP1114881A4 (fr) 1999-06-18 2000-06-14 Film de carbone, procede de formation associe, article recouvert de ce film, et procede de preparation de cet article

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JP11172130A JP2000096233A (ja) 1998-06-20 1999-06-18 炭素膜及びその形成方法並びに炭素膜被覆物品及びその製造方法

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CN103374697B (zh) * 2012-04-20 2017-09-29 深圳富泰宏精密工业有限公司 类金刚石膜层的表面处理方法及制品
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WO2018211618A1 (fr) * 2017-05-17 2018-11-22 日産自動車株式会社 Coupelle cloche d'appareil de revêtement de type à atomisation rotative
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CN109750271B (zh) * 2019-02-27 2021-01-26 中国科学院兰州化学物理研究所 一种耐高温耐磨损振动筛橡胶球及其制备方法

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CN1313914A (zh) 2001-09-19
CN1170003C (zh) 2004-10-06
TWI227281B (en) 2005-02-01
KR20010085399A (ko) 2001-09-07
EP1114881A1 (fr) 2001-07-11
US6652969B1 (en) 2003-11-25
KR100436829B1 (ko) 2004-06-23

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